1 


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A REVISION  OF  THE  PROXIMATE  COMPOSITION  OF  RHAMNUS 

PURSHIANA 

BY 

FRED  WARD  ALWOOD 
B.  S.  University  of  Illinois,  1920 


THESIS 

Submitted  in  Partial  Fulfillment  of  the  Requirements  for  the 

Degree  of 

MASTER  OF  SCIENCE 
IN  CHEMISTRY 

IN 

THE  GRADUATE  SCHOOL 

OF  THE 

UNIVERSITY  OF  ILLINOIS 


1921 


UNIVERSITY  OF  ILLINOIS 


THE  GRADUATE  SCHOOL 


JUNE  4 192JL 


I HEREBY  RECOMMEND  THAT  THE  THESIS  PREPARED  UNDER  MY 


SUPERVISION  BY FRED  V/ARD  AL^VOOD 


C 


ENTITLED  . /I  LEVI! 


o: 


PURSHIANA 


BE  ACCEPTED  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR 


Recommendation  concurred  in* 


Committee 


on 


Final  Examination* 


*Required  for  doctor’s  degree  but  not  for  master’s 


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■ AUC^ 


ACKiroV/LaDGUdElHT 

I wish  to  express  my  appreciation  to  Dr. 
George  D.  Beal  under  whose  direction  and  ad'vice 
this  work  has  "been  carried  out.  The  success  and 
results  are  due  largely  to  his  helpfulness  and 
suggestions  given  in  carrying  out  the  experimental 
Y/ork  of  this  paper. 


J 


Digitized  by  the  Internet  Archive 
in  2015 


https://archive.org/details/revisionofproximOOalwo 


TABLil  0?  GOITTailTS 


Page 


I. 

IIIIHODUCIIOH 

3 

II. 

EISTOHICAL 

4 

III. 

EXPERILSETAL 

8 

A.  Water  Soluble  l-iatter 

12 

B.  Hot  Water  Extract 

15 

IV. 

SUMiAHY 

17 

V. 

BIBLIOGRAPHY 

19 

3 


llITRQDUCglOH 

The  work  undertaken  was  a continuance  of  work  done  last 
year  hy  the  author.  At  that  time  more  attention  was  given  to 
the  insoluble  resin  and  its  products.  The  \7ater  soluble  matter 
was  also  examined,  but  during  evaporation  of  the  solution  it 
caramelized,  making  identification  of  the  sugars  impossible. 

From  the  results  obtained  it  v/as  concluded  that  a portion 
at  least  of  the  anthraquinone  derivatives  are  present  as  gluco- 
sides,  or  in  some  other  combined  form.  The  work  on  the  water 
soluble  matter  was  continued  this  year  with  the  results  which 
follow  in  the  experimental  part  of  the  investigation. 


A f.  ■ r ill  'i#^'*  Tin  ■**“  ^ -i  T-  ■- 


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4 


IiISTORIC.'lL 


Since  the  latter  part  of  the  eighteenth  century,  there  have 
been  described  various  naturally  occurring  dyestuffs  which  are 
yellow  in  the  free  state  and  give  red  colors  with  alkalies.  These 
dyestuffs,  as  prepared,  by  early  workers,  were  not  chemical  individ- 
uals . 

(1) 

In  1858  De  La  Rue  and  Miller  isolated  pure  emodin,  and 
in  1875  Schmidt  (2)  distilled  aloes  ?/ith  zinc  dust,  obtaining 


methyl  anthracene.  I'his  was  the  first  real  evidence  of  the  struc- 

so 

ture  of  these  compounds,  and  remained  until  1911,  when  Fischer  and 
Sapper  (3),  and  Fischer,  Falro  and  Gross  were  able  to  prove  that 
the  hydrocarbon  obtained  from  chrysophanic  acid  was  B methyl  an- 
thracene . 

Oesterle  has  shov;n  (5)  that  emodin  monomethyl  ether  is 
usually  associated  with  chrysophanic  acid.  It  was  due  to  his  v;ork 
(6)  that  chrysophanic  acid,  aloe  emiodin  and  rhein  v;ere  shown  to  be 
different  stages  in  the  oxidation  of  the  same  hydroxymethyl  anthra- 
quinone,  while  emodin  is  a tri-hydroxy-methyl  anthraquinone . 

The  structure  of  aloe-emodin  was  nroved  to  be 

o 

This  structure  being  proved,  the  structures  of  rhein  and  chryso- 
phanic acid  were  established  as  follows:- 


Ctti-OV\ 


0^  ° OW 


^ ah 


0 


Vik  <mMi' 


.,_  ,"■■  ^ - --7 

_ . .: 

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»',  .f^-  Vi  -^ym 


5 


the  structural  formula  for  emodin  has  not 
heen  established  exactly,  but  a large  amount  of  work  has  been  done 
by  Jowett  1 Potter  (7),  Oesterle  and  Tisza  (8),  and  by  Oesterle, 
and  in  1915  (9)  he  came  to  the  conclusion  that  the  formula  was:- 


o 


Dohme  and  Iilnglehardt  (10)  in  1898  stated  that  cascara  does 
not  contain  emodin  as  such,  but  a glucoside,  yielding  emodin  on 
hydrolysis.  The  glucoside  v;as  prefaced,  by  first  extracting  the 
drug  with  chloroform  to  remove  the  fat,  and  then  with  80/d  alcohol. 
The  alcohol  was  distilled  off  and  the  residual  extract  taken  up 
with  water  and  precipitated  with  lead  acetate.  The  precipitate 
was  filtered  off,  stirred  with  hot  water  and  hydrogen  sulfide  passed 
in.  The  sulfides  were  filtered  off  and  the  solution  evaporated. 

This  filtrate  was  treated  with  lead  subacetate  and  the  precipitate 
decomposed  with  hydrogen  sulfide.  The  filtrate  from  the  sulfides 
was  evaporated,  to  dryness.  A hard  brovmish-red.  substance  v/as  ob- 
tained, which  would  only  be  crystallized  with  great  difficulty. 

They  tried  crystallizing  in  acetone  and.  ethyl  acetate,  but  only  ob- 
tained a fev;  dark  red  needles,  melting  at  237'^C.  They  stated  that 
it  was  not  emodin,  since  it  gave  no  purplish  color  with  caustic 
potash,  and  that  it  was  a glucoside  characteristic  of  the  drug. 

IIo  proof  of  the  purity  of  the  crystals  v/as  given.  It  v/ould 
be  expected  that  any  impurity  present  would  modify  the  color  re- 
action. Prom  this  it  would  appear  that  the  crystals  were  impure 
emodin.  llo  proof  is  furnished  of  the  glucosidal  character  of  this 
substance,  and  no  tests  for  sugars  were  made  previous  to  or  after 


6 


hydrolysis . 

Thorpe  and  Hiller  (11),  and  Beal  and  Gnnton  ha-7e  isolated 
the  glucoside  frangulin  from  frangiila  hark.  It  melts  at  225°  and 
yields  emodin  and  rhamnose  on  hydrolysis.  They  ha've  also  con- 
firmed the  formula  of  the  glucosides  as  C2]_H2Q0g.  On  hydrolysis 
and  addition  of  one  mole  of  water  it  yielded  the  products  given 

above.  C21K20O5  + ^2'^  ^^15%0^5* 

Beal  and  Gunton  have  also  succeeded  in  preparing  a rhamnoside 

\> 

of  emodin  hy  the  condensation  of  emodin  with  triacetyl  from  rhamnose 
in  the  presence  of  alkali.  The  product,  while  impure,  as  shown  hy 
an  indefinite  melting  point,  behaved  in  a manner  similar  to  frangu- 
lin, and  v;hen  mixed  with  the  supposed  frangulin  from  frangula  hark, 
gave  only  a very  slight  lowering  of  the  melting  point  of  the  mix- 
ture . 

Jowett  and  Potter  made  a detailed  examination  of  the  consti- 
tution of  the  hark,  special  attention  being  directed  to  the  results 
already  obtained  hy  other  investigators.  Where  definite  substances 
were  isolated,  their  purity  was  established,  if  possible,  by  chem- 
ical methods. 

The  details  of  the  experimental  work  are  somewhat  extended, 
so  only  a summary  of  the  results  will  be  given.  In  addition  to 
emodin,  an  isomeric  substance  was  isolated  melting  at  183°C,  insol- 
uble in  ammonia,  and  its  acetyl  derivative  melted  at  168°C.  Glu- 
cose was  proved  to  occur  in  the  bark. 

IIo  evidence  could  be  obtained  of  the  existence  of  chryso- 
phanic  acid  or  chrysarobin  in  the  bark,  or  of  glucosides  yielding 
on  hydrolysis  emodin  or  chrysophanic  acid.  It  was  found  that 


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7 


emodin,  although  insoluble  in  water,  was  soluble  in  the  aqueous 
extract  of  the  bark  and  that  it  was  extracted  from  such  a solution 
only  slowly  and  with  difficiilty  by  shaking  with  the  imiscible  sol- 
vents. After  treatment  v/ith  acids,  the  water  soluble  substances 
were  decomposed  with  formation  of  insolube  resins  and  the  emodin 
vjas  very  readily  extracted  from  such  a mixture. 

The  bark  contained  about  two  per  cent  of  fatty  or  waxy 
material,  which  consisted  of  rhamnol  arachidate,  free  arachidic 
acid,  and  substances  yielding  on  hydrolysis  linolic  acid,  and  myris- 
tic  acid.  The  name  rhamnol  has  been  assigned  to  the  alcohol 
melting  at  135^-156°,  which  is  combined  with  arachidic  acid  in  cas- 
cara. 


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8 


I^LXP^HIIvliilllTAL 

The  author's  attention  V7as  nov/  directed  towards  the  products 
of  the  hydrolysis  of  rhamnus  purshiana,  the  water  soluble  extract 
being  studied.  When  the  bark  was  extracted  in  a percolator  of  the 
ordinary  type,  the  extract  being  concentrated  by  almost  continuous 
heating  on  the  steam  bath.  An  excellent  yield  of  emodin  was  ob- 
tained on  extracting  the  dried  resin  with  ether.  When  another, 
and  much  larger,  portion  of  the  drug  was  extracted  in  the  Lloyd 
apparatus,  in  which  the  extract  after  having  been  rapidly  concen- 
trated was  immediately  chilled  and  kept  cold,  the  yield  of  emodin 
obtained  from  the  resin  by  direct  extraction  was  very  much  smaller. 

It  was  thot  that  the  difference  in  yield  might  be  explained 
by  assuming  the  presence  in  the  drug  of  an  emodin  containing  gluco- 
side,  or  other  derivative,  which  was  extracted  in  either  instance 
by  the  alcohol,  but  in  the  one  case  was  broken  do?;n  by  continuous 
heating,  yielding  emodin  which  was  easily  extracted  by  ether. 

The  purpose  of  this  investigation  was  to  study  the  water 
soluble  extract  and  to  attempt  to  establish  the  presence  of  a glu- 
coside  in  the  bark. 

The  material  used  for  the  examination  was  cascara  bark,  ob- 
tained through  Fuller,  liorrison  and  Company,  Wholesale  Druggists, 
of  Chicago.  The  drug  as  received  \vas  in  the  form  of  quills,  and 
was  ground  to  about  number  twenty  powder  in  a Kance  Mill.  The  drug 
was  moistened  with  alcohol,  placed  in  the  percolator  of  a Lloyd 
ilxtraction  Apparatus,  covered  with  95/^>  alcohol,  and  allowed  to 
macenate  twenty-four  hours,  after  which  percolation  was  begun,  and 
continued  until  the  dinig  v;as  completely  exhausted. 


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9 


Concentration  of  the  percolate  uas  carried  out  in  the  con- 
centrator of  the  extraction  apparatus,  and  was  continuous  during 
the  extraction.  This  concentrator  is  of  a type  making  use  of  the 
principle  of  surface  e'vaporation,  while  the  tendency  is  for  the 
heavier  concentrate  to  he  carried  hy  gravity  to  the  lov;er  portion 
of  the  concentrator,  thus  removing  it  from  the  heated  zone.  The 
extract  is  never  exposed  to  heat  for  any  period  longer  than  one 
minute,  and  is  in  addition  rapidly  cooled  hy  a water  Jacket  sur- 
rounding the  apparatus  immediately  helow  the  heater.  This  short 
period  of  heating,  coupled  with  rapid  cooling,  and  the  fact  that 
the  extract  is  at  no  time  brought  in  contact  v/ith  air,  leads  one  to 
believe  that  the  extract,  as  thus  obtained,  must  represent  most 
closely  the  actual  nature  of  the  extractives  as  they  are  present  in 
the  tissues  before  extraction. 

The  extract  obtained,  representing  the  total  alcohol  soluble 
material  of  the  bark,  was  reddish  brown  in  color,  thick  and  syrupy. 
This  was  mixed  with  enough  alcohol  to  make  a liquid  having  the  vis- 
cosity of  a rather  thin  syrup,  and  sufficient  "dT/o  hydrochloric 
acid  added  to  give  an  actual  acid  concentration  of  one  percent.  The 
flasK  was  placed  on  a steam  bath,  with  a large  funnel  in  the  neck 
of  the  flask  to  restrict  circulation  of  air  and  loss  of  solvent,  and 
heated  at  such  a rate  that  the  alcohol  simmered  gently.  The  heat- 
ing was  continued  for  twenty-four  hours,  twice  replenishing  the  al- 
cohol lost  by  evaporation.  At  the  end  of  that  period  the  alcohol 
remaining  was  distilled  off  until  a thick  viscious  extract  remained, 
and  this,  while  still  warm,  ?;as  poured  into  a large  volume  of  water 
contained  in  a stone  Jar,  the  water  being  vigorously  stirred  by 


10 


means  of  a "blast  of  air.  I'he  precipitate  obtained  was  a dense, 
sticky  mass,  dark  brown  in  color.  This  was  filtered  from  an  orange 
yellow  liquid,  washed  with  water,  and  examined  in  1919-EO,  with 
the  following  results. 

The  work  of  this  year  is  carried  on  as  a continuance  of  that 
of  last  year,  in  which  the  hydrolysed  resin  was  studied.  The  bark 
was  extracted  with  alcohol,  the  alcoholic  extract  hydrolyzed  for 
twenty-four  hours  with  1^  hydrochloric  acid  and  poured  into  water. 
The  resin  separating  out  was  studied  with  the  results  which  follow. 

The  precipitated  resin,  after  being  air-dried,  was  broken 
into  small  fragments  and  placed  in  the  inner  tube  of  a large  Soxh- 
let  extraction  apparatus,  where  it  was  extracted  with  ether.  The 
resin  during  this  extraction,  possibly  due  to  the  presence  of  a 
small  amount  of  water,  gradually  cohered  into  a gummy  mass,  only 
slightly  permeable  to  the  ether.  When  this  stage  was  reached,  the 
resin  -/as  removed,  dried  and  powdered  again,  then  returned  to  the 
extraction  apparatus  and  the  extraction  with  ether  completed.  The 
resin,  after  the  ether  failed  to  dissolve  more  material,  was  dis- 
solved in  alcohol,  hydrolyzed  a second  time  with  one  percent  hydro- 
chloric acid,  and  precipitated  and  extracted  with  ether  as  before. 

Since  the  anthraquinone  derivatives  present  in  the  ether  ex- 
tract would  differ  in  acidity  by  reason  of  variation  in  the  number 
of  hydroxyl  a«d  carbonyl  groups  present,  the  ether  solution  was 
shaken  with  solutions  of  progressively  increasing  basicity  in  order 
to  effect  a partial  separation.  Accordingly  the  ether  extract  was 
shaken  in  turn  with  solutions  of  ammonium  carbonate,  sodium  carbon- 
ate, and  sodium  hydroxide. 


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Ammonium  Carlonate  ij^xtract. 

Shaking  the  ether  solution  vjith  b^o  ammonium  carbonate 
yielded  a deep-red  soliition.  This  extraction  was  repeated  until 
the  carbonate  solution  became  only  slightly  colored.  The  extracts 
thus  obtained  were  combined  and  acidified  with  hydrochloric  acid, 
forming  a yellow  precipitate,  rather  small  in  'volume.  The  precipi- 
tate thus  obtained  was  recrystallized  in  part  from  alcohol  and  part- 
ly from  glacial  acetic  acid.  The  crystals  were  dried  in  air,  and 
melted  at  248°C.  uncorrected.  From  the  melting  point  of  the  com- 
pound this  was  found  to  be  emodin.  A mixture  vjith  an  equal  quan- 
tity of  emodin  from  other  sources  showed,  no  lowering  of  the  melting 
point . 

An  acetyl  derivative  was  prepared  by  refluxing  with  acetic 
anhydride  and  fused  sodium  acetate  for  one  hour.  On  cooling  the 
solution,  lemon  yellow  needles  appeared.  These  were  recrystallized 
from  glacial  acetic  acid,  which  after  drying  melted  at  197*^,  ■on- 
corrected.  This  corresponds  to  the  melting  point  and  appearance 
of  triacetyl  emodin  as  given  in  the  literature,  and  as  previously 
obtained  in  this  laboratory. 

Sodium  Carbonate  iixtract . 

The  ether  extract  was  then  shaken  out  with  b^o  sodium  carbon- 
ate giving  a deep-red  solution.  The  extraction  was  repeated  until 
the  sodium  carbonate  solution  was  only  slightly  colored.  The  ex- 
tracts were  combined  and  acidified  with  hydrochloric  acid  forming 
an  orange  yellow  precipitate,  large  in  volume.  The  precipitate  was 
filtered  and  recrystallized  from  glacial  acetic  acid.  The  melting 


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point  of  this  precipitate  was  250-255*^0.  This  was  shown  to  he 

emodin  by  the  method  previously  described.  The  triacetyl  deriva- 

0 

tive  prepared  as  before  gave  the  yellow  needles  melting  at  197  , 
corresponding  to  triacetyl  emodin. 

taodium  Hydroxide  iilxtract. 

The  ether  extract  was  shaken  out  with  a 5^  solution  of 
sodium  hydroxide  until  fresh  portions  of  alkali  added  took  on 
only  a slight  color.  The  extracts  were  combined  and  acidified 
with  sulphuric  acid,  forming  a dark  brovm  precipitate,  very  small 
in  volume.  The  precipitate  was  recrystallized  from  glacial  acetic 
acid.  On  attempting  to  determine  the  melting  point  of  this 
material,  it  darkened  greatly  and  apparently  decomposed,  making  it 
impossible  to  observe  the  true  melting  point,  The  value  lies 
above  260OG. 

The  water  soluble  extract  was  treated  and  clai^ified  for 
examination  last  year,  but  on  evaporating  the  solution  caramelized 
making  any  further  identification  impossible.  It  was  due  to  this 
fact  that  the  following  work  was  carried  out. 

The  orange  yellow  filtrate,  on  standing  in  a closed  con- 
tainer, gradually  deposited  a lemon  yellow  precipitate.  This  was 
filtered  off,  and  the  filtrate  evaporated  to  a small  volume  under 
a diminished  pressure. 

A.  Water  Soluble  Hatter. 

The  filtrate  from  the  hydrolyzed  resin  was  filtered  and 
neutralized  with  barium  carbonate,  and  filtered  again.  The  fil- 
trate was  evaporated,  under  diminished  pressure,  to  a small  vol- 


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ume  and  filtered. 

The  precipitates  obtained  were  dried  and  united,  and  ex- 
tracted in  a Soxhlet  apparatus  with  ethyl  ether.  The  ether  ex- 
tract was  shaken  out  siiccessively  with  5^  solutions  of  ammonium 
carbonate,  sodium  carbonate  and  sodium  hydroxide.  T'rom  the 
ammonium  carbonate  extract,  after  acidifying,  only  a small  amount 
of  amorphous  red  resin  was  obtained.  The  sodium  carbonate  ex- 
tract yielded  emodin  v/hich  was  recrystallized  from  glacial  acetic 
acid  and  was  identical  with  the  emodin  described  in  the  litera- 
ture. The  sodium  hydroxide  extract  did  not  yield  anything. 

The  filtrate  was  treated  with  lead  acetate  and  a precipi- 
tate, large  in  volume,  was  obtained.  The  filtrate  was  treated 
with  hydrogen  sulphide  to  remove  the  excess  lead,  and  the  lead 
sulphide  filtered  off.  This  solution  was  evaporated  under 
diminished  pressure,  passing  carbon  dioxide  through  the  solution 
during  the  evaporation.  A portion  of  this  solution,  after  re- 
moval of  the  excess  hydrogen  sulphide,  was  tested  to  determine 
the  amount  of  sodium  hydroxide  necessary  to  neutralize  the  acid 
present.  Then,  to  the  remainder  of  the  solutions,  a little  less 
than  the  amount  needed  to  neutralize  was  added.  This  solution 
was  evaporated  under  diminished  pressure,  watching  closely  for 
any  signs  of  caramelization  or  formation  of  a product.  A dark 
brown  resinous  substance  separated  out  during  the  evaporation. 

This  was  filtered  and  dried,  but  no  melting  point  could  be 
obtained.  The  filtrate  was  diluted  with  five  volumes  of  absolute 
alcohol,  but  no  product  crystallized  out.  This  solution  was 
allowed  to  evaporate  spontaneously,  but  nothing  separated  out  ex- 


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14 


cept  more  of  the  dark  brown  resin.  A portion  of  the  solution 
was  evaporated  to  dryness,  and.  some  crystals  separated  out,  but 
on  examination  it  was  found  to  be  sodium  acetate. 

The  solution  was  tested  for  the  presence  of  sugars  by  the 
Molisch  napthol  test.  A few  drops  of  the  solution  were  diluted 
v;ith  water,  and  to  this  was  added  napthol  in  chloroform  solution; 
concentrated  sulfuric  acid  was  poured  down  the  side  and  a ring 
was  formed,  which  is  characteristic  of  sugar  solutions. 

An  attempt  was  then  made  to  make  an  osazone  by  boiling 
some  of  the  solution  with  phenyl  hydrazine  hydrochloride  and 
sodium  acetate,  llo  product  of  osazone  could  be  obtained.  A 
brown  precipitate  separated  out,  but  on  trying  to  recrystallize 
from  50/O  alcohol  nothing  vms  obtained. 

A portion  of  the  solution  was  then  tested  with  I’ehling's 
solution  to  see  if  there  vjas  any  reduction.  A precipitate  of 
red  cupious  oxide  was  obtained  showing  that  sugars  might  possibly 
be  present.  The  reduction  of  the  Fehling's  solution,  however, 
may  be  due  to  some  other  constituent  in  the  clarified  solution. 

The  precipitate  formed, on  the  standing  of  the  water  soluble 
extract  of  the  hydrolyzed  resin,  was  dissolved  out  of  the  con- 
tainers with  95%  alcohol.  The  alcohol  v/as  then  distilled  off, 
after  extraction  with  ether,  and  recovered.  The  ether  extract 
was  in  turn  shaken  out  with  ammonium  carbonate,  sodium  carbonate, 
and  sodium  hydroxide.  The  ammonium  carbonate  and  sodium  hydroxide 
solutions  on  acidifying  yielded  nothing.  The  sodium  carbonate  on 
acidifying  gave  a brown  precipitate.  This  precipitate  was  re- 
crystallized from  alcohol,  most  of  the  precipitate  going  into 


15 


solution  leaving  a small  amount  of  yellow  substance,  which  did 
not  go  into  solution.  This  v;as  filtered  off,  dried  and.  identified, 
as  emodin. 

B.  Hot  Y/ater  iixtract. 

A hot  water  extraction  of  the  ground  hark  was  made  and  ex- 
amined. The  extract  was  dark  brown  in  color  and  was  evaporated 
under  dimiinished  pressure  to  a small  volume  and  clarified  by  add- 
ing lead  acetate  and  sodium  phosphate,  the  phosphate  being  added 
to  remove  the  excess  lead,  thus  doing  away  with  the  use  of  hydro- 
gen sulphide  and  subsequent  evaporation  of  the  excess  hydrogen 
sulphide.  This  solution  was  evaporated,  further  to  see  if  anything 
?/ould  crystallize  out,  but  only  a dark  brown  substance  came  down. 
The  solution  did  not  yield  any  precipitate  on  attempting  to  pre- 
pare an  osazone,  but  did  reduce  Fahling's  solution  forming  the 
characteristic  red  cuprous  oxide. 

The  precipitate  formed  on  standing  of  the  extract,  and  the 
precipitate  from»  the  clarified  solution  was  treated  with  acid  and 
hydrolyzed  for  twenty-four  hours,  but  no  test  for  sugars  was  ob- 
tained on  examination  of  the  solution. 

An  attempt  ?/as  made  to  isolate  the  glucoside  as  Dohme  and 
Bnglehardt  did  in  1898.  The  solution  was  treated  v/ith  lead 
acetate  and  filtered.  This  precipitate  was  taken  up  in  hot  water 
and.  hydrogen  sulfide  was  passed  in.  The  sulfides  were  filtered 
off  and  the  filtrate  treated  v;ith  lead  subacetate.  The  precipi- 
tate was  filtered  off,  taken  up  ?;ith  hot  water  and  hydrogen  sul- 
fide passed  in  to  decompose  the  precipitate.  The  filtrate  from 
the  sulfides  was  evaporated  to  dryness.  A dark  brownish-red  sub- 


16 


stance  was  obtained.  An  attempt  to  determine  the  melting  point 
was  made,  but  could  not  be  determined. 


17 


^UluivIARY 

The  follov/ing  conclusions  -were  drawn  from  the  preceding 

year’s  Vi/ork  on  the  resin; 

1.  Powdered  cascara  was  extracted  under  such  conditions 

that  the  extract  coiilcl  he  concentrated  with  the  minimum  amount 
of  exposure  of  the  concentrated  material  to  heat,  thus  avoiding 
decompositi on. 

2«  The  extract  so  obtained  was  hydrolyzed  in  alcoholic 

solution  by  means  of  one  percent  hydrochloric  acid. 

3.  The  resin  precipitated  from  this  solution  showed  the  pre- 
sence of  a larger  amount  of  emodin  than  the  unhydrolyzed  extract. 

4.  The  presence  of  sugar  in  the  water  soluble  extract  from 
the  hydrolyzed  resin  was  shovm,  but  the  sugar  was  not  identified. 

5.  Prom  the  results  obtained  it  is  concluded  that  a portion, 
at  least,  of  the  anthraquinone  derivatives  are  present  as  gluco- 
sid.es,  or  in  some  other  combined  form.. 

The  following  conclusions  are  dravm  from  the  work  of  this 

year  on  the  v;ater  soluble  extract  of  the  hydrolyzed  resin. 

1.  The  material  separating  out  in  the  containers  of  the 
v;ater  soluble  extract  was  examined  and  found  to  contain  emiodin. 

2.  The  filtrate  from  this  material  was  neutralized,  clari- 
fied, and  evaporated  under  diminished,  pressure,  but  only  a dark 
brown  resinous  substance  separated  out. 

3.  The  solution  gave  a test  for  sugars  with  Llolisch  alpha 

duct 

naphthol  reagent,  but  on  testing  for  osazone  formation,  no  pro- 
was  obtained. 


18 

4.  On  lolling  some  of  the  solution  with  Fehling’s  solution 
a large  precipitate  of  cuprous  oxide  was  obtained,  showing  the 
presence  of  sugars. 

5.  The  hot  water  extract  of  the  hark  v/as  clarified  and  test- 
ed for  sugars,  hut  no  osazone  could  he  obtained. 

6.  On  attempting  to  isolate  the  glucoside,  as  Dohme  and 
iinglehardt  did,  only  a dark  hrovmish-red  substance  vms  obtained. 
It  did  not  correspond  with  the  substance  which  they  obtained. 

7.  ITrom  these  results  it  is  concluded  that  sugars  are  present 
in  the  water  soluble  extract,  but  they  could  not  be  isolated. 

(O 

It  does  not  seem  probably  that  the  glucoside  can  be  isolated  by 
methods  which  have  been  used. 


19. 


BIBLIOGHAiPHY 


(1) 

Am.  J.  Pharm.  30  (1858)  442-447 

(2) 

Ber.  8 (1875)  1274 

(3) 

J.  Prakt.  Chem.  83  (1911) 

203 

(4) 

Ibid.  83  (1911)  208 

(5) 

Aroh  de  Pharm.  243  (1905) 

434;  248 

(1910) 

(6) 

Proc.  Amer.  Pharm.  Assoc. 

45  (1897) 

193 

(7) 

Trans.  Chem.  Soc.  (1903) 

1329 

(8) 

Arch  de  Pharm.  246  (1908) 

114 

(9) 

Arch  de  Pharm.  252  (1915) 

327 

fic) 

J.  Amer.  Pharm.  Assoc.  45 

(1897)  198-202 

(11) 

J.  Chem.  Soc.  61  (1891) 

1. 

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